Electrospray Ionization Mass Spectrometry (ESI-MS) monitoring of the photolysis of diazinon in aqueous solution: Degradation route and toxicity of by-products against Artemia salina

The photolytic degradation of diazinon, an organophosphorus pesticide, in aqueous medium under assorted pH values was continuously monitored by direct infusion electrospray ionization mass spectrometry (ESI-MS). The results indicated that the UV radiation was quite efficient in promoting the pesticide degradation at the three pH levels evaluated (5, 7 and 8). The m/z of the most abundant ions observed in the mass spectra (MS), in conjunction with the fragmentation patterns of such ionic species (MS/MS data), made possible the proposition of chemical structures for the main by-products formed. As a result, routes for the photodegradation of diazinon in aqueous solution could thus be suggested. In the assays using Artemia salina (brine shrimp) it was verified that the photodegradation products exhibited much lower toxicity than the primary substrate. Aiming at mimicking the conditions ordinarily found in water treatment plants, an additional series of tests was conducted with a solution containing sodium hypochlorite and diazinon. This solution, when not exposed to UV radiation, exhibited high toxicity against the microorganisms. Under the influence of UV radiation, however, the toxicity rates decreased dramatically. This result is relevant because it points toward the confident application of UV radiation to neutralize the deleterious effects caused by diazinon (and perhaps other organophosphorus pesticides) as well as sodium hypochlorite to the environment.     

The effect of soil:water ratios on the induction of isoproturon, cypermethrin and diazinon mineralisation

The rate of pesticide biodegradation does not remain constant with time, and is dependent on the physico-chemical properties of the soil and of the pesticide as well as on the biology of the soil. Prolonged or repeated contact between soil microbes and pesticides has been shown to result in an increase in the rate and extent of biodegradation. This work assessed the impact of the soil:water ratio on measurement of catabolic induction for ¹⁴C-isoproturon, ¹⁴C-diazinon and ¹⁴C-cypermethrin. Slurrying (1:1 and 1:3 soil:water) with agitation resulted in significantly higher rates and extents of mineralisation than the non-slurried system (P ? 0.05; 1:0 soil:water), except for the mineralisation of ¹⁴C-diazinon where the greatest extent of mineralisation occurred in non-slurried soil. Slurrying without agitation resulted in the significant lower mineralisation in all cases (P ? 0.05). There was a significant interaction between the soil:water ratio and length of contact (P ? 0.05). Whilst the use of slurried systems can enhance the extent and rate of mineralisation, there is no improvement in reproducibility, and so for the measurement of catabolic induction, the use of field conditions will lead to a more environmentally relevant measurement.     

Chemical fate,latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment: A modeling assessment

Cyclic volatile methylsiloxanes (cVMS) such as octamethycyclotetrasiloxane (D4), decamethycyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are widely used as intermediates in the synthesis of high-molecular weight silicone polymers or as ingredients in the formulation of personal care products. The global environmental fate, latitudinal distribution, and long range transport of those cVMS were analyzed by two multimedia chemical fate models using the best available physicochemical properties as inputs and known persistent organic pollutants (POPs) and highly persistent volatile organic chemicals (“fliers”) as reference. The global transport and accumulation characteristics of cVMS differ from those of typical POPs in three significant ways. First, a large fraction of the released cVMS tends to become airborne and is removed from the global environment by degradation in air, whereas known POPs have a tendency to be distributed and persistent in all media. Secondly, although cVMS can travel a substantial distance in the atmosphere, they have little potential for deposition to surface media in remote regions. This contrasts with a deposition potential of known POPs that exceeds that of cVMS by 4–5 orders of magnitude. Thirdly, cVMS have short global residence times with the majority of the global mass removed within 3 months of the end of release. Global residence times of POPs on the other hand are in years. The persistent fliers resemble the cVMS with respect to the first two attributes, but their global residence times are more like those of the POPs.